No description available.

An ion-specific electrode measured cupric ion activity modulated by fulvic acid (FA) and pH in a series of modified Frog Embryo Teratogenesis Assay- Xenopus (FETAX) toxicity assays. Hydrogen ion concentration was the primary determinant of cupric ion activity, while FA played a smaller but significant role. Fulvic acid was a weak copper complexing agent at pH 5.50. At pH 5.50 there was slight reduction of ionic activity and a subsequent attenuation of copper toxicity with 5.0 mg/L FA. At pH 7.50, FA also had a mild attenuating effect on copper toxicity. At pH 6.50, copper was strongly complexed by FA at total copper (TCu) concentrations below its pH-dependent solubility limit. At TCu concentrations above the solubility limit FA enhanced toxicity. There was more cupric ion activity measured in the presence of 0.5 and 5.0 mg/L FA than without it at TCu concentrations above the solubility limit. The proposed mechanism for this behavior was FA action as a nucleation inhibitor. Under the chemical conditions of the pH 6.50 experiments, a stable supersaturation of copper was formed, resulting in a more toxic aqueous matrix.

Organisms living in aquatic environments are subject to a number of stressors from natural (temperature, predation, food availability) and anthropogenic origins (pesticides, metals, etc). Natural stressors may amplify the effects of contaminants and increase an organism’s sensitivity to them. Understanding the impact of these combined factors is therefore essential for the practical management of contaminants. This study sought to examine how predatory cues affect copper tolerance in the mosquitofish, Gambusia affinis. The influence of predatory cues on fish metabolic rate was also evaluated to gain insight on any interactive effects between the natural stressor and copper. Alarm cues, chemicals released into the water when prey are injured were obtained from humanely sacrificed G. affinis, and kairomones, passive cues released by predators, were obtained from adult bluegill (Lepomis macrochirus). Paired 96-h toxicity tests with copper and predatory cue and with copper alone were conducted to determine the influence of predatory cues on G. affinis sensitivity to the metal. In the presence of alarm cue neither G. affinis copper tolerance or metabolic rate was altered. At copper concentrations ranging from 0.25mg Cu/L - 0.50mg Cu/L kairomone presence had no influence on survival, while between 0.50mg Cu/L and 1.0mg Cu/L, kairomone presence increased survival. Kairomone had no significant effect on metabolic rate. The apparent antagonistic effect between kairomone and copper may have resulted from the presence of organic material from predator-derived cues or from potential changes in fish behavior. This study adds to the growing body of literature which illustrates the complexity of stressor interactions in aquatic systems.

Some species of marine phytoplankton are believed to be more tolerant of high concentrations of trace metals than others, but no conclusive test of this hypothesis has been conducted. Eleven species of phytoplankton representing 5 classes were grown in Aquil medium containing Cd$ sp{2+}$ concentrations between 10$ sp{-9.85}$ and 10$ sp{-6.84}$ M. Growth rates and intracellular concentrations of Cd, C, N and S were measured. Cadmium quotas (mol Cd/litre-cell volume) were lower in members of Bacillariophyceae than in Chlorophyceae, Prymnesiophyceae, Dinophyceae and Cyanophyceae (ANOVA, p $<$ 0.001). Cellular C:S molar ratios decreased in phytoplankton grown at high (pCd 7.37-6.84) compared to low Cd (no added Cd), as S/litre-cell volume increased. Similar results were observed for C:N molar ratios. In two species that were examined, C:S ratios decreased as a linear function of increasing Cd concentration. Mean Cd$ sp{2+}$ concentration that reduced growth rate to 50% of maximum (pCd$ sp{50})$ was not significantly different among phytoplankton classes (ANOVA, p $<$ 0.05). When these experimental data were combined with pCd$ sp{50}$s calculated from published sources, Chlorophyceae were found to be the most resistant class (ANOVA, p $<$ 0.01). Cadmium and Cu resistance (pCd$ sp{50}$ and pCu$ sp{50})$ were correlated (r = 0.52, p $<$ 0.05), suggesting co-tolerance of phytoplankton to toxic levels of these metals. Chlorophyceae were most tolerant and Cyanophyceae the least tolerant of Cu (ANOVA, p $<$ 0.01). No significant differences were observed among Bacillariophyceae, Prymnesiophyceae, and Dinophyceae, which were of intermediate sensitivity to both metals. The results confirm the existence of a phylogenetic dependence of resistance to trace metal toxicity in phytoplankton.

No description available.

Two studies were conducted to evaluate the effectiveness of using copper sulfate (CuSO4) as a drench in Hampshire ewes to control stomach worms (Haemonchus contortus). A study was conducted to assess the effectiveness of CuSO4 to control gastrointestinal nematodes (GIN) over a three year period. Ewes were FAMACHA scored, hematocrit evaluated for packed cell volume (PCV), and fecal egg counts (FEC) were determined from 2007 through 2009. Ewes received only CuSO4 to control GIN. Ewes with FEC exceeding 6,000 eggs/g feces were drenched. A separate study during the summer of 2008 assessed the potential of CuSO4 drench to cause copper toxicity in Hampshire ewes. Eighty-four ewes were blocked to one of two treatments according to parity and balanced for FEC. One group received CuSO4 (D) and the other was not drenched (ND). Jugular blood samples were collected at pre-determined intervals after CuSO4 was administered to D ewes. Serum was analyzed for aspartate aminotransferase (AST), alanine aminotransferase (ALT), and creatine kinase (CK). Elevated serum levels indicate copper toxicity. Results suggest CuSO4 has the potential to control stomach worms in Hampshire ewes without causing copper toxicity.

Copper oxide nanoparticles (NPs) are used in an expanding range of industries including a potential for agricultural applications as a fungicide. Accidental spills or misapplication of CuO NPs may lead to soil contamination. Plant roots exude a wide range of organic chemicals for bioprotection and to enhance bioavailability of nutrients. Many of these chemicals are metal chelators that may increase the solubility of CuO NPs, thus enhancing the impact of these NPs on plants. This work was directed towards understanding which plant exudates force increased solubility of CuO NPs and to determine if the level of NP in the growth matrix drives a feedback effect, regarding composition and quantity of exudates. Wheat seedlings (Triticum aestivum cv Deloris) were grown in a sand matrix for 10 days after 3 days of germination. The sand was amended with sublethal doses of CuO NPs from 0 to 300 mg Cu/kg dry sand. Sand was selected as the solid growth matrix as a proxy for soil in terms of plant root morphology, mechanical impedance and water stress, while providing a low background of dissolved organic carbon for the isolation of root exudates. After plant growth, the pore water was collected from the sand by vacuum filtration and analyzed. By coupling analytic techniques including Triple Quad Mass Spectroscopy and ion chromatography with geochemical modeling, we have identified citrate and the phytosiderophore, deoxymugineic acid (DMA) as chelators that drove the majority of dissolution of CuO NPs, especially DMA at higher CuO NP doses. Altered biogeochemistry within the rhizosphere was correlated with increased plant uptake of Cu and bio-response via exudate type, quantity and metal uptake. Exposure of wheat to CuO NPs lead to dose-dependent reduction in Fe, Ca, Mg, Mn and K in roots and shoots. This work is relevant to growth of commercially important crop wheat in the presence of CuO NPs as a fertilizer, fungicide or a pollutant.

Contaminants may affect marine organisms through various pathways with impacts evident across a variety of spatial and temporal scales. Organisms may encounter short pulsed exposures which contaminate surface waters for hours to days, or more persistent but patchy contamination of benthic habitats throughout their entire life-cycle. This thesis examines the responses of epifauna associated with macroalgae to a pulsed exposure of contaminants (storm-water input) and to chronic contamination via metal accumulation within temperate algal beds. The effects of storm water were monitored during a two-year survey of Sydney Harbour which sampled epifauna before and after heavy rainfall. Epifaunal assemblages declined throughout the harbour following storm events but for the most part these declines were not attributable to storm-water runoff. However, transient (&lt 4 d) and localized impacts of storm water upon physico-chemical characteristics of recipient water and some epifaunal groups were identified around storm drains. A novel field dosing technique tested the relative importance of freshwater and associated metals as causative agents of behavioural avoidance and direct mortality responses. Strong avoidance of storm-water plumes was found which could be entirely explained by freshwater inundation, with no additional effects of metals. No direct mortality was observed following brief exposures. Contaminants introduced by storm water may accumulate within the tissues of macroalgae and potentially pose persistent threats to epifauna. Colonisation of epifauna was reduced on algae with enhanced copper levels, and the nesting behaviour, feeding and survival of an abundant amphipod were all negatively affected by copper load. Subsequent field surveys identified sufficient copper, lead and zinc contamination in Sydney Harbour algal beds to pose direct toxic threats to epifauna. The abundance of herbivorous amphipods correlated negatively with the copper content of a common algal species. However, differences in metal accumulation between algal species resulted in spatially variable levels of contamination. Small-scale patchiness of contaminants within these landscapes may allow populations of mobile species to persist if contaminated hosts are avoided. In summary, epifaunal assemblages appeared resilient to storm-water pulses. Recovery of affected groups was rapid and large fluctuations in abundance appear to be part of the natural flux of epifaunal communities. In contrast, assemblages responded strongly to algal-bound contaminants and this has emerged as an important pathway of contaminant exposure and impact within algal habitats.

Contaminants may affect marine organisms through various pathways with impacts evident across a variety of spatial and temporal scales. Organisms may encounter short pulsed exposures which contaminate surface waters for hours to days, or more persistent but patchy contamination of benthic habitats throughout their entire life-cycle. This thesis examines the responses of epifauna associated with macroalgae to a pulsed exposure of contaminants (storm-water input) and to chronic contamination via metal accumulation within temperate algal beds. The effects of storm water were monitored during a two-year survey of Sydney Harbour which sampled epifauna before and after heavy rainfall. Epifaunal assemblages declined throughout the harbour following storm events but for the most part these declines were not attributable to storm-water runoff. However, transient (&lt 4 d) and localized impacts of storm water upon physico-chemical characteristics of recipient water and some epifaunal groups were identified around storm drains. A novel field dosing technique tested the relative importance of freshwater and associated metals as causative agents of behavioural avoidance and direct mortality responses. Strong avoidance of storm-water plumes was found which could be entirely explained by freshwater inundation, with no additional effects of metals. No direct mortality was observed following brief exposures. Contaminants introduced by storm water may accumulate within the tissues of macroalgae and potentially pose persistent threats to epifauna. Colonisation of epifauna was reduced on algae with enhanced copper levels, and the nesting behaviour, feeding and survival of an abundant amphipod were all negatively affected by copper load. Subsequent field surveys identified sufficient copper, lead and zinc contamination in Sydney Harbour algal beds to pose direct toxic threats to epifauna. The abundance of herbivorous amphipods correlated negatively with the copper content of a common algal species. However, differences in metal accumulation between algal species resulted in spatially variable levels of contamination. Small-scale patchiness of contaminants within these landscapes may allow populations of mobile species to persist if contaminated hosts are avoided. In summary, epifaunal assemblages appeared resilient to storm-water pulses. Recovery of affected groups was rapid and large fluctuations in abundance appear to be part of the natural flux of epifaunal communities. In contrast, assemblages responded strongly to algal-bound contaminants and this has emerged as an important pathway of contaminant exposure and impact within algal habitats.

A doença de Wilson (DW) é rara, de herança autossômica recessiva, com prevalência estimada de 1 em 30.000 nascidos vivos, causada por distúrbio no metabolismo do cobre, com sede no fígado e que causa acúmulo do metal primeiramente no hepatócito e secundariamente em outros tecidos (encéfalo, córnea, rins e outros). Os objetivos deste trabalho foram: comparar os achados da espectroscopia de prótons por ressonância magnética (ERM) dos pacientes com DW aos do grupo controle em três localizações (núcleos da base, substância branca frontal e córtex parieto-occipital); correlacionar o grau de acometimento neurológico (através de um escore) e a ERM nos núcleos da base (NB); e correlacionar as imagens convencionais de ressonância magnética (IRM), mensuradas também através de um escore, e a ERM nos NB. Avaliamos 34 pacientes com DW (idades: 13-43 anos) usando seqüências multiplanares ponderadas em T1, T2 (eco de spins e eco de spins rápido) e FLAIR; e a ERM nos três locais do cérebro, feita pela técnica STEAM (stimulated echo acquisition mode), com tempo de eco curto e volume de interesse único. O grupo controle (n= 37, idades: 12-43 anos) foi submetido basicamente ao mesmo protocolo. As ERMs foram pós-processadas e obtidas as relações: NAA/Cr, Co/Cr, mI/Cr e Glx/Cr; o escore neurológico foi feito atribuindo-se uma nota de 0 a 3 para 13 sinais e sintomas mais freqüentes na DW, variando entre 0 e 39; e o escore das IRM foi feito atribuindo-se 1 ponto para cada estrutura acometida com hipersinal em T2, hipossinal em T2 e/ou hipersinal em T1, variando entre 0 e 17. Comparamos as relações entre os metabólitos estudados nas ERMs dos pacientes e controles, e observamos que os pacientes apresentaram, de forma estatisticamente significativa: redução da relação NAA/Cr nos três locais, indicando perda neuronal (NAA é um marcador neuronal), embora possa haver um componente reversível da redução desta relação relacionado a um distúrbio funcional neuronal, sem perda celular, principalmente em pacientes em início de tratamento; aumento da relação mI/Cr nos NB, sugerindo gliose (mI é um marcador glial), que é observada nos NB na DW em estudos anátomo-patológicos. Observamos ainda aumento da largura média dos picos nos NB, provavelmente por deposição de ferro e cobre nestas estruturas, observada na DW. Tentamos estabelecer correlações entre as relações nos NB, em especial as relações NAA/Cr e mI/Cr, e o escore neurológico dos pacientes, não se obtendo correlação estatisticamente significativa. Tentamos também correlacionar estas relações e o escore das IRM, encontrando-se apenas correlação fraca, embora estatisticamente significativa, entre a relação mI/Cr e o escore, provavelmente explicado pelo fato de que tanto esta relação pode ser um marcador de gliose, quanto o escore analisa estruturas com hipersinal em T2 que ao menos em parte correspondem a áreas de gliose. Assim, notamos que a ERM demonstrou claramente alterações bioquímicas nos pacientes quando comparados ao grupo controle; e que houve correlação, embora fraca, entre as IRM e a ERM nos NB (relação mI/Cr), possivelmente porque ambas, ao menos em parte, se modificaram em resposta à gliose observada nos NB na DW / Wilson\'s disease (WD) is rare, with autossomal recessive inheritance, and an estimated prevalence of about 1 in 30,000 of the population, caused by an abnormality in copper\'s metabolism, which is located in the liver and which leads to a deposit of this metal first in the hepatocyte and in extrahepatic tissues (brain, cornea, kidneys and others) afterwards. The objectives of this work were: compare the findings of proton magnetic resonance spectroscopy (MRS) in patients with WD to a control group in three locations (basal ganglia, frontal white matter and parieto-occipital cortex); make correlations between the degree of neurological impairment (measured by a score) and MRS in basal ganglia (BG); and make correlations between conventional magnetic resonance imaging (MRI), measured also by a score, and MRS in BG. We evaluated 34 patients with WD (ages: 13-43 years) using multiplanar T1, T2 (spin echo and fast spin echo) and FLAIR-weighted sequences; and MRS in the above mentioned three areas of the brain, using STEAM (stimulated echo acquisition mode) technique, with a short echo time and in single voxel mode. The control group (n= 37, ages: 12-43 years) was submitted to basically the same protocol. The spectra were post-processed and the following ratios were obtained: NAA/Cr, Co/Cr, mI/Cr e Glx/Cr; the neurological score was made by attributing to the 13 signs and symptoms more frequently observed in WD a 0-3 grade, with a 0 to 39 variation; and the MRI score was calculated by ascribing 1 point to each structure presenting high signal in T2-weighted images, low signal in T2-weighted images and/or high signal in T1-weighted images, varying from 0 to 17. We compared the metabolites\' ratios studied in patients and controls\' MRS, and we observed that patients presented, in a statistically significant way: decrease of the NAA/Cr ratio in the three areas, indicating neuronal loss (NAA is a neuronal marker), although a reversible component of this ratio\'s decrease might coexist, related to a functional neuronal disturbance, without cellular death, mainly during the beginning of the treatment; increase of the mI/Cr ratio in BG, suggesting gliosis (mI is a glial marker) that is observed in pathological studies with respect to the BG in WD. We also observed an increase in the mean width of the peaks in BG, probably secondary to copper and iron deposition that occurs in these structures, observed in WD. We tried to establish correlations between the BG ratios, specially NAA/Cr and mI/Cr, and the patients\' neurological scores, and we found no statistically significant correlation. An attempt was made also in obtaining correlations between these ratios and MRI scores, and we found only a weak, although statistically significant, correlation between mI/Cr ratio and MRI score, probably residing in the fact that this ratio can be considered a gliosis marker, and the MRI score analyses structures with high signal in T2-weighted images that at least partially correspond to areas presenting gliosis. So, we noticed that MRS clearly demonstrated biochemical alterations in WD patients when compared to controls; and that a significant correlation, although weak, was found concerning MRI and MRS in BG (mI/Cr ratio), possibly because both, at least partially, changed in response to gliosis that is observed in the BG in WD